Phenolic comdensation product and procres of manufacturing



' FRANK P.

srarnspra rsnr OFFICE.

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PERIODIC GOIDBI'BAi'l-IOI mDUC'! m .10 Drawing.

To all whom it may concern:

Be it known thatwe, Lswmmon' V. Reousx, a citizen of Canada, (who has taken out his first papers for citizenship in the United States,) residing at Evanston, Cook county, .Ill. and Ancnm J. Wsrrn and moon, citizens of the United States, residing at Chicago, in the county of Cook and State of Illinois, have invented a new and useful Improvement in Phenolic Condensation Products and Processes; of Manufacturingbf which the following is a specification.

This invention relates particularly to the production of phenolic condensation products and especially molded products.

As is kIlOWll, a phenohc condensation roduct is produced by combining a phenolic ody, such as phenol or its homo ogues with an active methylene substance, such as examethylenetetramin or formaldehyde, containing the methylene radical.

It is well known that a phenolic condensation product (usually having a filler introduce therein) may be molded in hot presses and discharged hot or cold, as desired. It

has been proposed, also, to mix a phenolic condensatlon product with a filler and mold Y the same in the regular manner of coldefi'ected the action of heat after its removal from the molded products, the final hardening being y subjecting the molded article't'o mold. In a prior art patent, it is pro osed to pre are an initial roduct ofdpheno and forma de'hyde (the atter in ecided excess); arrest the-reaction when a soluble resin of sp. produced; mix this binder with a filler; and

- then mold the mixture and harden by heat mass to be properly kneade treatment. This calls for a reaction in the molded product in which water is formed as a by-product andv must be eliminated by heat, tending to the production of a spongy and otherwise inferior product; Moreover, difiiculty has j been experienced in securing resins of proper 'conslstenc to permit-the properly molded by a cold-molding process.

his is due artly to the formaldehy e, and the difiicult of determining the loss of methylene. v t has been proposed, also, 101, acetone, etc., in an efiortto secure the proper consistency and the proper coherency specification of Letters Patent.

Application fled lane 6, 1918. Serial Io. 88,478.

mentioned 1n said r. from 1.15 to 1.21 has been- .ucts has proven practicable,

and afterward volatile nature of to use such solvents as alcoin the molding operation, but this involves additional expense for materials not useful in the product and is otherwise objection able, and especially so because of the difficulty of securing the resin in a stage of reaction at which it is best adapted for the purpose.

Another very serious objection to the process described in the above-mentioned patent is that a phenol-formaldehyde resin avmg a specific gravity within the limits ggtent corresponds with a reaction roduct tween phenol and formaldehy e, taken in the proportionstated 1n the patent, which is about two-thirds (or more) complete; that is to. say, the lowest limit (sp. gr. 1.15) mentioned in the atent eorres onds with a phenol formal ehyde resin m which about of the phenolic bod has combined with the .forma dehyde, whi e the upper limit (s gr. 1.21) corresponds with such a resin having about 80% of the phenolic body combined with the formaldehyde. This means that the reaction has roceeded too far. to permit of proper we ding of the particles in a quickmolding process, assuming that a properad Patented May 4, 1920.

mixture of the binder with a filler could be possible. The desirability of eliminating water formedas a byroduct (as well as water of solution) lea to this difiiculty. The result is an almost worthless product having very low tensile strength, a low dielectric constant, and high water-absorptive qualities.

So far as we are aware, no method of cold-molding phenolic condensation prodor' found its use. Our primary a thoroughly practicable henolic condensation way into practic ject is to provide method whereby products may be sub ected to a short moldmg operation at ordinary or room temperatures, and subsequently hardened by heat treatment after removal from the molds.

ice

By such a method, the output of the molds may be increased as will be immediately appreciated, this re sults in an enormous savin in the cost of molds, the cost of presses, t e costof labor,

and inothe cost of production, generally.

The difiiculties indicated above may be obviated, and excellent moldedcompounds from 50 to 75 fold; and,

- comprising or containing a phenolic oondensation product may be produced by the im roved process herein described.

he. improved process, in a referred example, may be described as fol ows: A suitable filler, either an organic filler or an inorganic filler, such. as wood flour or asbestos pulp or fiber, or a combination of an orgame and an inorganic filler, if desired, is

moistened with a solution of hexamethy-.

lenetetramin in'a fresh unreacted phenolic body, such as cresol; and afterward there is added 'a potentially. reactive phenolic condensation product, preferably in pulverulent form, anhydrous in character and. capable of anhydrous reaction, which is thoroughly mixed with the moistened filler, thus roducing a suitable molding composition. he hexamethylenetetramin, the ore potentially reactive phenolic condensation product constitute a blnder which is capable of being hardened by heat treatment into a. hard resistant and substantially infusible and insoluble condensation product.

The mixture of the fillei and binder is introduced into a mold and subjected to a heavy molding pressure at ordinary or room temperature, or at any desired temperature. This pressure is desirably from three to five tons per square inch, and the molding operation re uires butan instant. article is then removed from the mold and sub'ected to heat treatment for a suflicient period of time to convert the molded article to a hard resistant body, the binder becoming, in this step of the treatment, practica ly infusible and insoluble when the heat treatment is sufficiently long continued.

The heat treatment is preferably continued for a period of several hours, usually .from two to twenty hours, depending upon conditions, including the size of the molded article, etc. Also, the heat treatment is preferably graduated, starting with a temperatureap roximating room temperatures, and being e evated either continuously or from time to time until a temperature of say 160 C. to 200 C. is reached, after which the treatment may be continued at such temperature for several hours. Care should be exercised to prevent the application of too much heat immediately after the molded article is introduced into the kiln. The molding composition is such as to enable the molded article to properly retain its form, but the quick application of too much heat may result in an imperfect article. The object which is to be attained in this respect 1s to so gradually expel solvents (where present) and ammonia during the first portion of the heat treatment as to harden the molded body and cause it to require such tenacity as to enable the article to retain its form and avoid blistering. With the exercise' of moderate care, this may be readily and the The molded assess;

accomplished and after the body has gained a desired tenacity in the preliminary heat treatment, the tem rature may be raised 'quite rapidly unti the maximum desired phenol resins. A very satisfactory product is produced by employin the materials in the proportion of 30% binder and 7.0% asbestos filler, for illustration.

More specifically describing the preferred method, take 50 pounds of cresol dissolved with 13 pounds of hexamethylenetetramin and mix the same with 600 pounds of. asbestos pulp and 150 pounds of asbestos 'fiber, preferably about one-half inch in length. Mix these together in any suitable machine, such as a kneading machine, referably at about room temperature. fter such mixing operation, add 300 pounds of a fusible condensation product of henoland hexamethylenetetramin, preferab y pulverulent, such condensation product preferably containing therein both free phenol and free hexamethylenetetramin. Mix these materials intimately in the kneading machine, thus producing a moldin compound which is suitable for introduction into the molds. In the proportions given, the moldin compound will be found to be of a consistency. suitable for molding, will flow properl in themolds, and will possess sufficient co erency to enable the material to be properly compacted in the molds and to retain the shape imparted by the molds. Should the molding compound be found to be too dry, suitable solvents may be added, though generally not necessary; and should the molding material be found to be too 'wet or sticky, it may be brought to the desired consistency by gentle heatin Where solvents are usetfi any of the usual solvents for soluble phenolic condensation products may be employed, such as alcohol, acetone, or a mixture of solvents. If de-' sired, some water may be used in the solvent or mixture of solvents. In any case, the Whole mass,- before introduction into the molds, is kneaded until it has become a homogeneous plastic. It is then pressed in the molds, which either may be hot or cold, or

at temperatures ranging say from 100 C. so

to 160 C. or higher. At the outset of the heat treatment, it is preferred to apply the heat with moderation until the molded article acquires such tenacity as to resist blistering or deformation of form. The molded article preferably is kept at a higher temperature noted for a period of several hours, or until the chemical reaction has proceeded to a point which will give the maximum desired qualities. Assuming the phenolic body and methylene body to be used in the proper proportions (corresponding with approximately one methylene group to each phenolic group) the phenolic condensation product,'at the end of the heat treatment, will be practically infusible and insoluble.

It has been observed that where a warmed or moderately heated mold is em loyed, say a mold having a temperature 0 90 C. to 120 C., a better surface is attained in a rapid molding process than is attained when a cold mold is employed. The molds may be of any desired temperature, however,

which will not interfere with the rapid operation and in any case the main chemical reaction which must occur to complete the transformation of the binder to the hard infusible state may be performed after the removal of the molded article from the mold. This enables vast economy to be effected in the production of molded articles comprising or containing a phenolic condensation product. If desired, the stock may be warmed preparatory to the molding operation.

Where it is desired to produce a flameproof molded article, one may employ 30% .by weight of binder and by weight (or more) of asbestos filler. We have succeeded in producing such a flame-proof product, and our invention in this respect meets a long-felt want. A flame-proof product requires in excess of sixty percent. by weight of inorganic filler.

The fusible phenolic condensation product which we prefer to employ as a part of the binder in the manner describedabove is preferably produced as follows Mix 1080 pounds of cresol (2CH C I-I OH) and 140 pounds of hexamethylenetetramin (CH ),,N,; heat the mixture in a vessel or still, while stirring, to a temperature of 140 (1; then turn off theheat and allow the evolution of ammonia to proceed (the.

temperature automatically rising); apply further heat after the rapid evolution of ammonia ceases, continuing the heat at a temperature of preferably 165 C. for twelve to twenty-four hours; then raise the temperature gradually through a period of from. four to seven hours, reaching a temperature of about 215 C. and then discontinue the heat; then eliminate or drive off a portion of the free cresol, perhaps ten per cent. or more of the original amount, by

blowing hot air'through the fusible mass while in liquid condition, leaving a resin which corresponds with about 19 phenol roups to each methylene group; then pour into or mix with the blown mass 7 8 pounds of creosote oil, and also pigments or coloring matter, if desired; pour the mass into a mixer, such as a paint-mixer, the mass being now at a temperature of from 85 C. to 125 C. and having the consistency of a stiff liquid or tafl'y; add to, or stir into the mass 120 pounds of hexamethylenetetramin ground into or partially dissolved in creosote oil, say about thirty-six pounds ofoil, and also, if desired, a small amount of fats, fatty acids, or waxes, preferably three to six per cent. by weight; and finally cool the potentially reactive resin (now containing both free cresol and free hexamethylenetetramin). in pans; and break up or comminute the material, say to pass through a (SO-mesh screen, or finer.

Having inthis manner produced an anhydrous potentially reactive resin which is capable of anhydrous reaction, mix the same with the previously prepared asbestos, that is, the asbestos mixed with hexamethylenetetramin disssolved in cresol, as described above. This mixing operation may be performed in a'dough-mixer, which results in warming the mass. Additional creosote oil,

in small quantity, may be added, if n'ecessary, to get the proper consistency and plasticity, the mass being now somewhat 1n the condition of a. putty.

The material is then cooled, and broken up or pulverized, say to pass a 10-mesh screen; and in this condition the material is ready for molding.

In the example of a molding compound produced as described above, it is to be noted that of the total binder used in the compound at least substantially one-half (in the illustration given, more than one-half) of. the binder comprises a free or unreacted )henolic body and a free methylenebody. t is desirable that a minor portion, or not substantially more than one-half, of the binder should be in the form of a phenolic condensation product, as otherwise the most perfect welding or coalescence of the particles of the molding compound will not be obtained in a quick-molding operation. ()bviously, the proportions may be varied withsubjected to heat treatment to render them hard, resistant, and .tenacious.

If desired, the molding material may be rolled intosheets, and'these sheets may be 5 warmed on a steam-table preparatory to balling the material and introducing it into the mold, in accordance with a. well-known method of molding plastic sheet material. However, this step is unnecessary; and usuall it is undesirable.

. he proportions used in compounding the materials to make the fusible, soluble resin are such as to afford about ten phenolic groups'to six methylene groups; and, after the blowing process, the proportions are preferably about nine phenolic groups to six methylene groups. with one mol. of hexamethylenetetramin to nine mols. of the phenolic body. The proportions may be varied somewhat, but it'is desirable, in the final product, to have the proportions such as to aflford about one phenolic group to each methylene group. Thus, where hexamethylenetetramin is used,

the final product corresponds to somewhere between 5.5 mols. of the phenolic body to 6.5 mols. of the phenolic body to each 'mol.- of hexamethylenetetramin. Preferably, the final compound corresponds with about 6.3 mols. of the phenolic body to each mol. of the hexamethylenetetramin, or slightly greater than the molecular ratio. Where the molded article can be subjected economicall to a prolonged heat'treatment it is desira le to have a slight excess of phenol rather than an excess of hexamethylenetetramin at the beginning of the heat treatment.

The creosote oil employed is a commercial 40 creosote oil. It is ahydrocarbon solvent of high boiling point, obtained by distillation of coal tars, asphalts, etc., and comprises cyclic hydrocarbons mainly. Such a slowly volatile solvent is useful in giving to the fusible resin a desirable spreading and penetrating quality, and results in an improved product of increased tensile strength. vThe creosote oil remains partly in the product,

desirabl tempering the product. Any suitable so vent. having these characteristics may be employed. The boiling points of solvents obtained by distillation of coal -tars,-etc., may

about 235 C. Such a solvent is useful in keeping the molding materials in condition for molding for a considerable period of time after they have been produced.

As has been pointed out, the fusible phenolic condensation product described above is anhydrous in character; and when mixed with hexamethylenetetramin is capable of hardening by an anhydrous reaction, with the evolution of ammonia.

A less desirable method of producing a 66 soluble phenolic condensation product which The latter corresponds.

vary from about 130 C. to

may be used in the practice of the im roved process herein described, is to mix a enolic body and formaldehyde (40% solutlon) and a catalytic agent, if desired, using about 1?; phenohc groups to each methylene group; 70

boil the mixture until the methylene has combined with the phenolic body; eliminate the water by drawing ofi, orby boiling, or by both; blow off a' sufficient amount of the "phenolic body to give a resin corresponding to about 1% phenolic groups to each methylene group; and having, in this manner, obtained a substantially anhydrous fusible phenolic condensation product, proceed as above by mixing creosote oil and hexamethylenetetramin with the resin, the hexamethylenetetramin being insufiicient quantity to afford, in the final product, about one phenolic group to each methylene roup. It will be seen that thismethod a ords a substitute 8i for the soluble anhydrous resin procured by reacting directly upon a phenolic body wit a methylene-amin body scribed above.

Another variation of. the process, which eliminates the preparatory forming .of a phenolic condensation product, is as folows: Take 75 pounds of hexamethylenetetramin dissolved in 300 pounds of cresol ;mix the same with 600 pounds ofasbestos pulp and 150 pounds of asbestos fiber, this operation preferably'being performed in a kneading machine; proceed with the kneading opera-v tion until a thoroughly homogeneous mass is produced. This material may be molded without the addition of an initial condensation product. Such a mixture molds readigy and forms easily'to the required shape. t has not,- however, the stiff plasticit which allows it to maintain its form an at the same time be removed'easily from the mold, especially in more complex forms. The desired stiffness and coherency can be produced, however, by the addition of small amounts of suitableresins dissolved in suit: able solvents. For example, asphalt or coal tar pitch may be dissolved in benzol and added to the mixture. The-pro ortion of v such resins employed may vary. n the case of asphalt, one may advantageously use 10% of the weight of cresol. Other natural resins, such as copal, kauri, etc, may be used in suitable proportions to give the desired consistency to the plastic. In any case, a percentage of creosote oil,,or similar material may be' added. if desired. The materials ma be molded at ordinary temperatures un er pressure, or in moderately heated molds; and the molded product may be converted to a hard resistant body by suitable prolonged heat treatment. A good example of proportions is 75% of asbestos filler, 20% of a binder composed of a mixture of hexamethylenetetramin and a phe-- in the manner derasaiat nolic body, and 5% of coal tar pitch, these proportions being by weight.

Instead of producing a fusible phenolic condensation product in the manner first described herein, we may proceed inthe manner described in United States Letters Patent No. 1,242,593, granted Oct. .9, 1917,

using initially about nine mols. of cresol to" each mol. of hexamethylenetetramin, and

mixing creosote oil'with these materials initially or after the reaction has been effected. Such fusible phenolic condensation product ma be mixed with hexamethylenetetramin an subsequently mixed with the filler, pro-.

ceeding in the manner suggested above.

Any suitable fillers may be used in the moldmg compound, such as asbestos, mica, flock, wood pulp, etc.; and the physical condition of the molding material may vary greatly, depending upon the articles to be teristic which prevents injury to the dies in the molding operation. In other words, this 'molding compound can be used without wearing off the. sharp edges or corners of the dies, so that sharp outlines in the molded product may be secured for an indefinite time, and for a very large number of operations without renewing the dies. This is a ver Y important consideration, and the result is doubtless due to the fact that the great body of the molding compound retains the solvent, even after there has been an apparent surface evaporation from the particles, or pellets, which make up the compound, so that the compound retains perfect plasticity and will not cut the dies, even though the molding operation be not performed for a considerable time after the compound has been prepared. readily volatile solvent, such as alcohol, acetone, or the like, to be employed, the

result would be not only that the molding f compound would not possess the necessary degree of plasticity to enable it to flow prop: erly and weld properly in the dies, but, also, the compound would cause the dies to Wear out rapidly in the molding operation.

Ashereinbefore stated, phenol, or a homologue, or any suitable phenolic body, may be employed in practisin the process. Recognized equivalent pheno ic bodies in the art are, for example, phenol, the. cresols, and the xylenols. The most desirable active methylene body for use in the process is the methylene-amin compound hexamethylenetetramin. -Another instance of a methylene-amin compound which might be used in the process is hydrobenzamid or benzaldehyde amin. It may be stated, how- Were a ever, that this latter substance is too expensive at the present time to be. economically employed in the process.

he foregoing detailed description has been given for clearness of understandin only, andno unnecessary limitations shoul be understoodv therefrom, but the appended claims should be construed as broadly as permissible, in view of the prior art.

What we regard as new and desire tosecure by Letters Patent is 1. The process of producing a phenolic .condensation product article, which comprises: mixing initially a fibrous filler and raw materials for a binder comprisin a phenolic body in unreacted state; ad mg and mixing therewith a fusible phenolic-f condensation product, the mixture being sup lied with an anhydrously reacting met ylene body in sufficient quantity to convert the binder to a hard and substantially infusible state; molding the materials thus compounded under heavy pressure at ordinar or moderate temperature for a relative y short period of time; and then subjecting the molded article to heat treatment after removal from the mold until it becomes hard, resistant and substantially infusible.

2. The process of producing a molded phenolic condensation product article, which comprises: mixing a fibrous filler and a binder comprising a fusible phenolic condensation'product, a phenolic body and a methylene substance adapted to re-act anice hydrously, said binder materials being proportioned to form a hard and substantially infusible condensation product and at least approximately half the binder com rising v free phenolic body and free methy ene substance; molding the materials thus compounded under pressure at ordinar or desired temperature for a relatively s ort period of time; and then subjecting the molded article, after removal from the mold, to prolonged heat treatment until a hard and substantially infusible body readapted to react anhydrously therewith;

compacting the materials and forming a body without substantially hardening the same; and subjectin such body to prolonged heat treatment unti the binder is converted to a hard, resistant and substantially infusible state. 1

4. The process of producing a molded phenolic condensation product article, which comprises: mixing initially a filler and a phenolic body and a meth lene body which is capable of acting anhy rously with said I phenolic body to form a condensation prodcondensation product being taken in greater uct; adding and mixing therewith a phenolic condensation product, the phenolic proportion than said phenolic body, the materials of the binder being taken in proportions adapted to produce a hard and substantially infusible condensation product;

phenolic condensation product article, which comprises: mixing initially a filler and a phenolic body and hexamethylenetetramin; adding and mixing therewith asubstantially anhydrous phenolic condensation product containing free phenol, the binder containing also a suflicient amount of hexamethylenetetramin to convertthe binder to a hard and substantially infusible state; subjecting the materials thus compounded to a quick-molding operation under pressure without substantially hardening the same; and then 'subjectirig the molded body to heat treatment out of the mold until the binder is converted to a hard, resistant and substantially infusible state.

6. The process of producing a phenolic condensation product, which comprises: mixing a fibrous filler, a binder comprising a fused phenolic condensation product, a phenolic body and a methylene-amin substance adapted to combine anhydrously therewith, and a solvent for the binder having a high boiling point, said binder materials being proportioned to react to form a hard and substantially infusible condensation product and at least approximately one-half of the binder comprising a free phenolic body and a free methylene substance; compacting said materials. into a body without substantially hardening the same; and subjecting such body to prolonged heat treatment until it'becomes hard, resistant and substantially infusible.

7, The process of producing a phenolic condensation product, which comprises: mixing a fibrous filler, abinder. com rising a fused phenolic condensation pro uct, a

' phenolic body and a methylene-amin sub-- stance adapted to combine anhydrously therewith, and a solvent for the binder comprising cyclic hydrocarbons and containing no readily reactive group, said binder materials being proportioned to react to form a hardand substantially infusible condensation product and at least approximately one-half of the binder comprising a free phenolic body and a free methylene substance; compacting said materials into a body without substantially hardening the same; and subjecting such body to prolonged heat treatment until it becomes hard, resistant and substantially infusible.

8. The process of producing a phenolic condensation product article, which com-- prises: mixing to ether initially a filler, a phenolic body and a'methylene-amin body adapted to re-act anhydrously therewith; adding and mixing therewith a fusible phenolic condensation product and including in the mixture a suflicient amount of methylene-amin substance to complete the .tively small quantity of a hydrocarbon solvent of high boiling point; subjecting the material thus compounded to a quick-molding operation under heavy pressure; and subjecting the molded article, after removal from the mold, to prolonged heat'treatment to produce a hard, resistant and substantially infusible body.

10. The process of producing a phenolic condensation product, which comprises:

mixing together a filler and a binder com prising a fused substantially anhydrous phenolic condensation product having incor orated therein a large excess of phenolic b0 y, a hydrocarbon solvent of compara-' tively hi h boiling point and a methyleneamin su stance adapted to combine with" the fused condensation product by an anhydrous reaction, the materials of said binder being proportioned to give ultimately a hard and substantially infusible product and the free phenolic body and free methylene-amin substance constituting at least approximately one-half the bindersubjectin to a quic molding operation at high pressure; and COIIVGItIII the molded product, after removal from the mold, to a hard, re-

. sistant and substantially infusible body by prolon ed heat treatment.

11. he process of producing a molded the materials thus compounded binder comprising a fused, substantially anhydrous phenolic condensation product'con- 5 taming a large excess of phenol, and hexamethylenetetramin in suiiieient quantity to combine with the fused condensation prod-' uct and give a hard and substantially in fusible product; subjecting the materials thus compounded to a quick-molding operation at high pressure without substantial hardening; and converting the molded product, after removal from the mold, to a hard, resistant and substantially infusible state by prolon ed heat treatment.

12. he process of producing a phenolic condensation product, which comprises:-

mixing together a filler and a binder comprismg a fused substantially anhydrous 4 subjectin amin substance adapted to combine with the fused condensation product by an anhydrous reaction, the materials of said binder being proportioned to give ultimately a hard and substantially infusible product; the materials thus compounded toa quic -molding operation at high pressure; and con-vertin the molded product, after removal from t e mold, to a hard,'re-

'sistant and substantially infusible body by prolonged heat treatment.

LAWRENCE V. 'REDMAN. ARCHIE .J. WEITH.

FRANKP. BROOK. 

